US5114983A - Use of polyarylene sulphides for the production of a structural foam resistant to high temperatures, process for the preparation of this foam, and moldings obtainable by this process - Google Patents

Use of polyarylene sulphides for the production of a structural foam resistant to high temperatures, process for the preparation of this foam, and moldings obtainable by this process Download PDF

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US5114983A
US5114983A US07/543,555 US54355590A US5114983A US 5114983 A US5114983 A US 5114983A US 54355590 A US54355590 A US 54355590A US 5114983 A US5114983 A US 5114983A
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foam
production
weight
high temperatures
preparation
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US07/543,555
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Kurt-Rainer Stahlke
William C. Bushong
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Bayer AG
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Bayer AG
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Assigned to BAYER AKTIENGESELLSCHAFT, A CORP OF GERMANY reassignment BAYER AKTIENGESELLSCHAFT, A CORP OF GERMANY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: BUSHONG, WILLIAM C., STAHLKE, KURT-RAINER
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/02Polythioethers; Polythioether-ethers

Definitions

  • the invention relates to the use of polyarylene sulphides (PAS), preferably polyphenylene sulphide (PPS), for the production of a structural foam, a process for the production of this foam, and mouldings obtainable by this process.
  • PAS polyarylene sulphides
  • PPS polyphenylene sulphide
  • thermoplastic injection moulding materials can be processed to mouldings or extrudates by the use of chemical or physical blowing agents with expansion in the mould using the structural foam injection moulding process.
  • thermoplastic moulding materials resistant to high temperatures can be prepared in a simple process.
  • the invention relates to the use of polyarylene sulphides (PAS), preferably polyphenylene sulphides (PPS), optionally as a mixture with fillers, for the production of structural foam.
  • PAS polyarylene sulphides
  • PPS polyphenylene sulphides
  • Polyarylene sulphides which can be used according to the invention are known (for example U.S. Pat. No. 3,354,129 and EP-A 171 021) and are commercially available (for example TEDUR®).
  • the polyarylene sulphides can be mixed from 0 to 80% by weight, preferably from 40-60% by weight (based on polyarylene sulphide) of fillers.
  • the fillers used may be organic and/or inorganic fillers, for example glass fibres, glass spheres, silicates, such as mice or talc, carbonates, such as a magnesium carbonate, sulphates, such as BaSO 4 or CaSO 4 , oxides such as TiO 2 , carbon fibres, aramide fibres, carbon, metals, metal fibres, etc.
  • the invention also relates to a process for the production of a structural foam, characterised in that 0.1 to 5% by weight of a blowing agent masterbatch is added to polyarylene sulphides, and the mixture is homogeneous and is expanded at 300° to 360° C., and mouldings obtainable by this process.
  • a blowing agent masterbatch is used. This contains 0.2-10% by weight of a chemical blowing agent, preferably 3-5% by weight.
  • the base resin used for this masterbatch is a partially crystalline or amorphous thermoplastic resin resistant to high temperatures, preferably a polycarbonate, such as Makrolon®, having a relative viscosity (in CH 2 Cl 2 , 25° C./ 0.5 g per 100 ml) of 1.260-1.285.
  • This blowing agent masterbatch is added to the polyarylene sulphide as the dry mixture in amounts of 0.2-5% by weight (based on PAS), preferably 08-1.5% by weight. Mixing is then carried out for 10-40 minutes, preferably 15-25 minutes, on a drum tumbler or other suitable mixing device.
  • the chemical blowing agents used for expansion are customary substances, for example azo compounds, such as azodicarboxamide, anhydrides, such as itaconic anhydride, azoles, such as 5-phenyltetrazole, etc.
  • customary "kickers" for example zinc oxide, can be used to accelerate the decomposition.
  • the polyarylene sulphide foam is produced at processing temperatures of 300°-360° C., which are usual for polyarylene sulphide (injection moulding or extrusion process), in the air under atmospheric pressure. If necessary, the procedure can be carried out in the absence of O 2 , under an inert gas, (for example N 2 ).
  • Mouldings produced in the structural foam moulding process from the above-mentioned mixtures have a uniform cell structure (see FIG. 1), the typical layer of a structural foam with uniform cell structure being observed. A density reduction of 35-50% by weight, preferably 40-45% by weight, is obtained in the moulding.
  • Mouldings produced according to the invention have the properties known for polyarylene sulphides, such as high heat resistance, rigidity, resistance to chemicals and low flammability.
  • 1% by weight of a masterbatch of a commercial polycarbonate having a relative viscosity of 1280 and 4% by weight of 5-phenyltetrazole are added to 10 kg of a polyphenylene sulphide prepared according to EP-A 171 021 and provided with 40% by weight of a commercial glass fibre, and mixing is carried out for 20 minutes on a drum tumbler. Processing is then carried out on a standard injection moulding machine under the conditions customary for the structural foam injection moulding process.
  • the mouldings obtained have a flexural strength of 120 N/mm 2 , an outer fibre elongation of 1.9%, a flexural modulus of elasticity of b 9000 N/mm 2 and an impact strength of 10 kg/cm 2 .
  • the heat distortion temperature HDT-A (1.81 N/mm 2 ) is 200° C.
  • the UL 94 (8 mm) classification gives VO (by our measurements).

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to the use of polyarylene sulphides (PAS), preferably polyphenylene sulphide (PPS) for the preparation of a structrual foam, a process for the production of this foam, and moldings obtainable by this process.

Description

The invention relates to the use of polyarylene sulphides (PAS), preferably polyphenylene sulphide (PPS), for the production of a structural foam, a process for the production of this foam, and mouldings obtainable by this process.
It is known that thermoplastic injection moulding materials can be processed to mouldings or extrudates by the use of chemical or physical blowing agents with expansion in the mould using the structural foam injection moulding process.
However, mouldings produced in the low pressure structural foam process (LPSF process) show only a small density reduction of 2-3% by weight (Plastic Design Forum July/August 1988). Another possibility for obtaining parts produced by the structural foam injection moulding process is described in EP-A 25 108. However, this process involves considerable chemical modifications (sulfphone carbonates, catalysts, heating).
Usually, however, mouldings or extrudates produced by the structural injection moulding process are produced by metering in a blowing agent masterbatch (see: Makrolon Polycarbonate Structural Foam brochure, Mobay Chemical Corp. 1985). However, the use of blowing agent masterbatches is often restricted since they must not expand during the preparation of masterbatches. On the other hand, a chemical blowing agent must undergo controlled decomposition in the structural injection moulding process so that a moulding is formed having a cell structure as uniform as possible. It is thus ensured that there cannot be any mechanically weak points with nonuniform foam structure.
The use of chemical blowing agents for the production of foamed thermoplastics resistant to high temperatures has been unsuccessful to-date for the above-mentioned reasons.
It has now been found, surprisingly, that thermoplastic moulding materials resistant to high temperatures can be prepared in a simple process.
The invention relates to the use of polyarylene sulphides (PAS), preferably polyphenylene sulphides (PPS), optionally as a mixture with fillers, for the production of structural foam.
Polyarylene sulphides which can be used according to the invention are known (for example U.S. Pat. No. 3,354,129 and EP-A 171 021) and are commercially available (for example TEDUR®).
For the production of the foam, the polyarylene sulphides can be mixed from 0 to 80% by weight, preferably from 40-60% by weight (based on polyarylene sulphide) of fillers. The fillers used may be organic and/or inorganic fillers, for example glass fibres, glass spheres, silicates, such as mice or talc, carbonates, such as a magnesium carbonate, sulphates, such as BaSO4 or CaSO4, oxides such as TiO2, carbon fibres, aramide fibres, carbon, metals, metal fibres, etc.
The invention also relates to a process for the production of a structural foam, characterised in that 0.1 to 5% by weight of a blowing agent masterbatch is added to polyarylene sulphides, and the mixture is homogeneous and is expanded at 300° to 360° C., and mouldings obtainable by this process.
In the production of the foam, a blowing agent masterbatch is used. This contains 0.2-10% by weight of a chemical blowing agent, preferably 3-5% by weight. The base resin used for this masterbatch is a partially crystalline or amorphous thermoplastic resin resistant to high temperatures, preferably a polycarbonate, such as Makrolon®, having a relative viscosity (in CH2 Cl2, 25° C./ 0.5 g per 100 ml) of 1.260-1.285.
This blowing agent masterbatch is added to the polyarylene sulphide as the dry mixture in amounts of 0.2-5% by weight (based on PAS), preferably 08-1.5% by weight. Mixing is then carried out for 10-40 minutes, preferably 15-25 minutes, on a drum tumbler or other suitable mixing device.
The chemical blowing agents used for expansion are customary substances, for example azo compounds, such as azodicarboxamide, anhydrides, such as itaconic anhydride, azoles, such as 5-phenyltetrazole, etc. Customary "kickers", for example zinc oxide, can be used to accelerate the decomposition.
The polyarylene sulphide foam is produced at processing temperatures of 300°-360° C., which are usual for polyarylene sulphide (injection moulding or extrusion process), in the air under atmospheric pressure. If necessary, the procedure can be carried out in the absence of O2, under an inert gas, (for example N2).
Mouldings produced in the structural foam moulding process from the above-mentioned mixtures have a uniform cell structure (see FIG. 1), the typical layer of a structural foam with uniform cell structure being observed. A density reduction of 35-50% by weight, preferably 40-45% by weight, is obtained in the moulding.
Mouldings produced according to the invention have the properties known for polyarylene sulphides, such as high heat resistance, rigidity, resistance to chemicals and low flammability.
These structural foams are used where, in addition to the properties familiar for polyarylene sulphides, weight reduction, thermal insulation and good flame-retardant properties are also important. Due to the good flowability of this resin, large sink free parts can be produced.
Applications for mouldings produced according to the invention are in the aviation and motor vehicle market, in the field of large partitions for thermal insulation and in the construction of chemical plants and apparatuses.
It is also possible to extrudates this material, in shapes, such as, pipes, sheets and other hollow articles. All mouldings and extrudates can be coated, metalised or adhesively bonded using known technologies or can be moulded by inserting metal parts or foils in an injection mould.
EXAMPLES Example 1
1% by weight of a masterbatch of a commercial polycarbonate having a relative viscosity of 1280 and 4% by weight of 5-phenyltetrazole are added to 10 kg of a polyphenylene sulphide prepared according to EP-A 171 021 and provided with 40% by weight of a commercial glass fibre, and mixing is carried out for 20 minutes on a drum tumbler. Processing is then carried out on a standard injection moulding machine under the conditions customary for the structural foam injection moulding process.
A structural foam having a uniform pore structure, a pore size of about 0.05 to 0.5 mm (see FIG. 1) and a specific gravity of 0.90 g/cm3 is obtained. A base resin which has a specific gravity of 1.65 g/cm3, corresponds to a density reduction of 45.5% by weight.
The mouldings obtained have a flexural strength of 120 N/mm2, an outer fibre elongation of 1.9%, a flexural modulus of elasticity of b 9000 N/mm2 and an impact strength of 10 kg/cm2.
The heat distortion temperature HDT-A (1.81 N/mm2) is 200° C. The UL 94 (8 mm) classification gives VO (by our measurements).
EXAMPLE 2
A resin described in Example 1 is mixed with 3% by weight of a blowing agent masterbatch described in Example 1 on a drum tumbler for 20 minutes. Injection moulded finished parts showed a weight reduction of 50% by weight (density=0.84 g/cm3).

Claims (1)

We claim:
1. Process for production of a molded article of polyalkylene foam which comprises homogeneous dry blending for 10 for 40 minutes polyarylene sulfide with 0.1 to 5% by weight of a blowing agent masterbatch which contains 0.2 to 10% by weight of a chemical blowing agent selected from the group consisting of azo compounds, anhydrides and azoles with or without zinc oxide, in an amorphous or partially crystalline polycarbonate resin resistant to high temperatures and having a relative viscosity of 1.260-1.285 measured in CH2 Cl2 at 25° C. at 0.5 gram per 100 ml, then at 300° to 360° C. foaming and molding the blended mixture by injection or extrusion molding.
US07/543,555 1989-07-05 1990-06-26 Use of polyarylene sulphides for the production of a structural foam resistant to high temperatures, process for the preparation of this foam, and moldings obtainable by this process Expired - Fee Related US5114983A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3922038A DE3922038A1 (en) 1989-07-05 1989-07-05 USE OF POLYARYL SULFIDES FOR PRODUCING A HIGH-TEMPERATURE-RESISTANT TSG FOAM, METHOD FOR PRODUCING THIS FOAM AND MOLDING OBTAIN THEREFORE AVAILABLE
DE3922038 1989-07-05

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US07/783,504 Division US5126380A (en) 1989-07-05 1991-10-28 Use of polyarylene sulphides for the production of a structural foam resistant to high temperatures, process for the preparation of this foam, and mouldings obtainable by this process

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US07/783,504 Expired - Fee Related US5126380A (en) 1989-07-05 1991-10-28 Use of polyarylene sulphides for the production of a structural foam resistant to high temperatures, process for the preparation of this foam, and mouldings obtainable by this process

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5412062A (en) * 1991-09-09 1995-05-02 Cookson Group Plc Thermally depolymerisable polyoxalate or polymalonate polymers containing hydrocarbon groups with 6-30 carbon atoms and a tertiary carbon atoms attached to bridging oxygen atom
US5547996A (en) * 1994-07-29 1996-08-20 The Center For Innovative Technology Method of producing foamed polymer materials
US5716999A (en) * 1994-08-15 1998-02-10 Hoechst Aktiengesellschaft Polyarylene sulfide foams and a process for their production
JP2013067735A (en) * 2011-09-22 2013-04-18 Tosoh Corp Master batch of foaming agent for polyarylene sulfide resin, method for producing the same, polyarylene sulfide resin composition and foam-molded product comprising the same
WO2018178323A1 (en) 2017-03-31 2018-10-04 Solvay Specialty Polymers Usa, Llc Foam material comprising polyphenylene sulfide polymer (pps)
US11286363B2 (en) * 2017-03-31 2022-03-29 Solvay Specialty Polymers Usa, Llc Foam material comprising polyphenylene sulfide polymer (PPS)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040175516A1 (en) * 1998-10-28 2004-09-09 Gerhard Schmitz Insulating arrangement for the inner insulation of an aircraft
WO2020180301A1 (en) * 2019-03-05 2020-09-10 Parker-Hannifin Corporation Tubular assembly comprising low density, low thermal conductivity low thermal effusivity polyarylene sulfide foam

Citations (7)

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US3925270A (en) * 1974-06-05 1975-12-09 Uniroyal Inc Polymeric composition comprising sulfonyl carbazates as blowing agents
FR2379370A1 (en) * 1977-02-08 1978-09-01 Philips Nv PROCESS FOR THE REALIZATION OF OBJECTS AT LEAST PARTLY IN THERMOPLASTIC MATERIAL FOAM, OBJECTS THUS REALIZED AND DEVICE FOR THE IMPLEMENTATION OF THIS PROCESS
FR2379910A1 (en) * 1977-02-08 1978-09-01 Philips Nv SEMICONDUCTOR DEVICE AND PROCESS FOR ITS COATING
US4183822A (en) * 1974-04-03 1980-01-15 Fisons Limited Blowing agent composition
US4263409A (en) * 1974-08-02 1981-04-21 General Electric Company Process for the production of a foamed thermoplastic composition
US4607059A (en) * 1985-09-25 1986-08-19 Pennwalt Corporation Gas-releasing composition for tailoring gas evolution of system IR 2811
US4804689A (en) * 1986-07-02 1989-02-14 Bayer Aktiengesellschaft Process for holding and foaming thermoplastic polyphenylene sulphide articles and the resultant products

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4183822A (en) * 1974-04-03 1980-01-15 Fisons Limited Blowing agent composition
US3925270A (en) * 1974-06-05 1975-12-09 Uniroyal Inc Polymeric composition comprising sulfonyl carbazates as blowing agents
US4263409A (en) * 1974-08-02 1981-04-21 General Electric Company Process for the production of a foamed thermoplastic composition
FR2379370A1 (en) * 1977-02-08 1978-09-01 Philips Nv PROCESS FOR THE REALIZATION OF OBJECTS AT LEAST PARTLY IN THERMOPLASTIC MATERIAL FOAM, OBJECTS THUS REALIZED AND DEVICE FOR THE IMPLEMENTATION OF THIS PROCESS
FR2379910A1 (en) * 1977-02-08 1978-09-01 Philips Nv SEMICONDUCTOR DEVICE AND PROCESS FOR ITS COATING
GB1594892A (en) * 1977-02-08 1981-08-05 Philips Nv Semiconductor devices and the provision of envelopes therefor
GB1600427A (en) * 1977-02-08 1981-10-14 Philips Nv Method of and apparatus for manufacturing an object consisting completely or partly of a foamed thermoplastic material
US4607059A (en) * 1985-09-25 1986-08-19 Pennwalt Corporation Gas-releasing composition for tailoring gas evolution of system IR 2811
US4804689A (en) * 1986-07-02 1989-02-14 Bayer Aktiengesellschaft Process for holding and foaming thermoplastic polyphenylene sulphide articles and the resultant products

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5412062A (en) * 1991-09-09 1995-05-02 Cookson Group Plc Thermally depolymerisable polyoxalate or polymalonate polymers containing hydrocarbon groups with 6-30 carbon atoms and a tertiary carbon atoms attached to bridging oxygen atom
US5547996A (en) * 1994-07-29 1996-08-20 The Center For Innovative Technology Method of producing foamed polymer materials
US5716999A (en) * 1994-08-15 1998-02-10 Hoechst Aktiengesellschaft Polyarylene sulfide foams and a process for their production
US5789452A (en) * 1994-08-15 1998-08-04 Ticora Gmbh Polyarylene sulfide foams and a process for their production
JP2013067735A (en) * 2011-09-22 2013-04-18 Tosoh Corp Master batch of foaming agent for polyarylene sulfide resin, method for producing the same, polyarylene sulfide resin composition and foam-molded product comprising the same
WO2018178323A1 (en) 2017-03-31 2018-10-04 Solvay Specialty Polymers Usa, Llc Foam material comprising polyphenylene sulfide polymer (pps)
US11286363B2 (en) * 2017-03-31 2022-03-29 Solvay Specialty Polymers Usa, Llc Foam material comprising polyphenylene sulfide polymer (PPS)

Also Published As

Publication number Publication date
EP0406634B1 (en) 1994-07-13
JPH03170536A (en) 1991-07-24
DE59006408D1 (en) 1994-08-18
DE3922038A1 (en) 1991-01-17
EP0406634A1 (en) 1991-01-09
US5126380A (en) 1992-06-30

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